Gasoline fuels



United States Pat en No Drawing. Application May 28, 1953 Serial No. 358,174

12 Claims. (Cl. 44-62) The present invention relates to improved fuel for inter- 2,834,662 Patented May 13, 1958 deposit-induced autoignitionor wild ping often produces deleterious effects inasmuch as it is a precurser of preignit1on.' -Therefore, wild ping results in rough engine operating conditions and very often increases the wear of engine'parts, piston burning and the like. In contrast to ordinary detonation, deposit-induced autoignition or wild ping cannot be satisfactorily controlled by retarding ignition timing norby operating under part throttle conditions. Inasmuch as automotiveengineeers are desirous of utilizing in internal' combu stion engines the highest compression "ratiospermitted by the commercially available'fuels, the

reduction of compression ratios to eliminate this problem nal combustion engines and, more particularly, to a 'class of motor fuel adjuvants which improve substantially the performance qualities of liquid hydrocarbon fuel.

is not desirable nor feasible. Indeed, it is the consensus of opinion among the designers of internal combustion 'engines that engine developments have heretofore been greatly'hinder'ed by the limitations imposed by deposit- "i'nduce'd autoignition It is evident, therefore, that the In recent years there has been a marked trend in the automotive industry of utilizing internal combustion and trucks. It has been found that this increase in compressionratio results in increased engine efiiciency whereby the motoring public is provided with both greater power availability and greater economy of operation.

engines having high compression ratios in passenger" cars present requirement for fuel having high antiknock qualities shall bgreatly surpassed by future requirements. Notwithstanding attempts to attain these qualities by alternative means, it is entirely probable that the most satisfactory method for the attainment of high octane fuels Highcompression engines almost uniformly require fuels of high octane number for most etficient operation." Of

the several methods of raising the octane number of gasoline developed to date, that of utilizing an an't'iknock agent, particularly of the organolead type, has been most successful. Although such antiknock agents have been 7 provided with corrective agents commonly known as scavengers,'which effectively reduce the amount of metallic deposits in the engine by forming volatile metallic compounds which emanate from the engine in the exhaust gas stream, the accumulation of engine deposits in combustion chambers and on other engine parts such as pistons, valves, and the like cannot be entirely prevented. This-accumushall continue to be the use of antiknock agents, particularly of the o'rganolead type. As a result, there is a paramou'nt need existing for a new and'improved method for altering the physical and chemical characteristics of deposits and for modifying the combustion process such that thedetrimental effects of deposit-induced 'autoignition' may be markedly suppressed or be eliminated.

Accordingly, it is an :object of this invention to provide adjuvants for leaded internal combustion engine fuel.

' Likewise, it is an objectof our invention to provide an im- 'provedcomposition adapted for use as fuel for internal combustion engines which,- when subjected to the combustion process, will result in the obviation of deposit-induced autoignition. Another object of the prese nt'inventionis to lation of deposits is particularly prevalent when the vehicles are operated under conditions of low speed and light load as encountered in metropolitan localities. As a result of the notable improvements in fuel :antiknockoua'lity,

which have been made in recent years, such deposits prese'nt but a few minor problems in low compressionengines, Whereas with engines of higher compression ratios two provide improved fluids adapted for blending with internal combustion engine fuel which concurrently prevent detonation or'knocking andobviate the deleterious effects of deposit-induced autoignition. Similarly, another object is toprovideprocesses for'improving the characteristics of internal combustion engine fuel. Likewise, an object of this invention is to provide processes of operating an inmore serious problems are becoming increasingly prevalent, those of detonation and deposit-induced autoignition or wild ping. Although detonation can successfully be obviated by the utilization of organolead antiknock agents such as tetraethyllead, it has been found that the severity of the wild ping problem often increases with the octane quality of the fuel. Hence, the automotive industry is faced with the dilemma resulting from the fact that each time the octane quality of the fuel is raised to' coincide with increases in compression ratio, deposit-induced autoignition generally becomes more severe.

Ordinary detonation in the internal combustion engine has been defined as the spontaneous combustion of an appreciable portion of the charge, which results in an extremely rapid local pressure rise and produces a sharp metallic knock. The control of ordinary detonation may be effected by retarding ignition timing, by operating under part throttle conditions, by reducing the compression ratio of the engine, and by using fuels having high antiknock qualities, that is, by using an organolead-containing fuel. Deposit-induced autoignition may be defined as the erratic ignition of the combustible charge by combustion chamber deposits resulting in uncontrolled combustion and isolated bursts of audible and inaudible 'manife's'tations of combustion, somewhat similar to knocking; Aside from organic magnesium material. I number of important and practical embodiments which will 0 terna l combustion engine which result in the suppression or minimization of wild ping. Additional important objects of this invention will become apparent from the discussion which follows.

' We have now found that the above and other objects of this invention can be accomplished by providing as adjuvants for leaded internal combustion engine fuel organic magnesium material. Likewise, a preferred embodiment of the present invention consists of providing improved compositions comprising organolead material and an Our invention involves a be considered in detail hereinafter.

In accordance with our invention We provide as adjuvants for leaded fuel for internal combustion engines a class of materials known in the art as organic magnesium materials. As used hereinafter the term organic magnesium material denotes organic magnesium-containing organic compounds, that is, compounds wherein mag- 'nesium is bonded indirectly to the carbon residue or orthe'nuisance experienced by the passenger car operator,

' ganic'portion of the compound through a linking element.

Such compounds are generally stable in common environments against the deleterious effects of atmospheric constituents, water, and the like because they are free'from carbont0-magnesium bonds. In general, We prefer essentially sulfur-free magnesium material in accomplishing the objects of this invention and in particular we'prefehcompoundscharacterized by the presence of magnesium-to oxygen bonds which can be ionic, coordinate or coordinate covalent bonds.

It will be apparent from the foregoing discussion that a preferred embodiment of this invention consists of providing improved compositions comprising organolead material and magnesium compounds formed with a member selected from the class consisting of chelating agents and organic compounds containing a replaceable hydrogen in an hydroxyl group. Therefore, the organic magnesium material utilized in accordance with the present invention is preferably a magnesium compound formed with a material selected from the group consisting of organic acids, phenols, alcohols and chelates.

As indicated the organic magnesium material we employ in the organolead-containing compositions of the present invention can exist in a number of chemical forms. By way of example in one embodiment of our invention We employ magnesium salts of organic acids. Such acids can conveniently be considered as consisting of seven general types. Thus, the magnesium salts of organic acids we employ in the organolead-containing compositions of the instant invention can be salts of saturated monobasic aliphatic carboxylic acids, monobasic unsaturated aliphatic carboxylic acids, dibasic aliphatic acids, polybasic aliphatic acids, aromatic carboxylic acids, naphthenic acids, and rosin acids.

When we employ as our organic magnesium material salts or soaps of saturated monobasic aliphatic carboxylic acids in accordance with this invention, we utilize the magnesium derivatives of such acids as caproic, oenanthic, caprylic, pelargonic, capric, undecylic, lauric, tridecylic, myristic, pentadecylic, palmitic, margaric, stearic, nonadecylic, arachidic, eicosanecarboxylic, behenic, lignoceric, cerotic, melissic, psyllastearic, and the like. In general, when employing such magnesium salts or soaps, we prefer those derived from acids containing from about to about 30 carbon atoms in the molecule since such compounds possess the desired solubility and inductibility characteristics, important criteria of the materials of the present invention.

Another class of magnesium derivatives of organic acids We employ in accordance with the present invention is the magnesium salts of monobasic unsaturated aliphatic carboxylic acids. Thus, we employ the magnesium compounds of such acids as erucic, oleic, citronellic, undecylenic, elaidic, ricinoleic, brassidic, nervonic, geranic, linoleic, 04-, and B-elaeostearic, linolenic, dehydrogeranic, stearolic, and like acids.

When we employ organic magnesium materials derived from dibasic aliphatic acids in the organolead-containing compositions of the present invention we utilize the magnesium compounds formed from such acids as suberic acid, azelaic acid, sebacic acid, nonane-dicarboxylic acid, decane-dicarboxylic acid, undecane-dicarboxylic acid, eicosane-dicarboxylic acid, phloionic acid, and like acids.

The polybasic aliphatic acids which form magnesium derivatives suitable for use in accordance with the present invention are exemplified by ethanetetracarboxylic acid, and the dialkyl and diaryl acid esters thereof. For example, we can utilize the magnesium compound formed from ethanetetracarboxylic acid per se and likewise we can utilize the magnesium derivatives of the diethyl ester of ethanetetracarboxylic acid. Similarly, we can use the magnesium compound derived from the diphenyl ester of ethanetetracarboxylic acid. Likewise, the aryl ester can be further substituted with alkyl groups so as to obtain the necessary balance of solubility and engine inductibility.

Another type of organic magnesium material which can be used in the organolead-containing compositions of the present invention is the magnesium salts of aromatic carboxylic acids. Such acids are exemplified by alkyl substituted benzoic acid, such as methyl benzoic acid, propyl benzoic acid, dimethyl benzoic acid, etc.; phenyl acetic acid, hydratropic acid, cinnamic acid, atropic acid, phthalic acid and alkyl substituted phthalic acids such as ethyl phthalic acid, butyl phthalic acid, diethyl phthalic acid, etc.; naphthalic acid and alkyl substituted naphthalic acids such as amyl naphthalic acid, octyl naphthalic acid, dihexyl naphthalic acid, the alkyl substituents being present in either of the aromatic rings or both; mellitic acids as, for example, the magnesium salt of mono alkyl esters of hemimellitic acid; and analogous acids.

Another class of organic magnesium material utilized in accordance with the present invention consists of the magnesium derivatives of naphthenic acids and other complex acid mixtures found in crude petroleum mineral oils. Magnesium naphthenate serves as an example of such substances.

The magnesium salts derived from rosin acids exemplify another class of organic magnesium material which can be utilized in organolead-containing compositions in accordance with the present invention. Rosin acids are complex acids derived from tall oil and pitch such as pine resin and the like; a common example of such acids being abietic acid.

Most of the magnesium salts derived from the above classes of acid substances are readily soluble in gasoline and in the constituents of antiknock fluids such as organolead compounds, organic bromine and/or chlorine scavengers and the like. By the same token, such magnesium compounds in general possess the characteristic of being readily inductible into the engine. Because of this it is generally unnecessary to utilize any of the common solubilizing agents such as coal tar fractions, petroleum cuts and the like although in some instances some additional benefits are to be derived by so doing.

Another embodiment of the present invention consists of utilizing in organolead-containing materials magnesium phenolates and closely related magnesium compounds. Such magnesium compounds can conveniently be considered as derivatives of monohydric phenols or of polyhydric phenols. In the former group we prefer to utilize such phenols as the diverse monohydroxy substituted benzenes, naphthalenes, hydronaphthalenes and the like as well as suitably substituted derivatives thereof. However, in general, we prefer to utilize the magnesium compounds formed by replacement of the hydrogen atom in the phenol group wherein the aromatic nucleus is substituted with alkyl side chains. Thus, we utilize the magnesium derivatives of such phenols as ortho, meta, and para-cresols, xylols such as 1,2-dimethyl- 3-hydroxy benzene, 1,2-dimethyl-4-hydroxy benzene, 1,3- dimethyl-Z-hydroxy benzene, 1,3-dimethyl-4-hydroxy benzene, 1,3-dimethyl-5-hydroxy benzene, 1,4-dimethyl-2- hydroxy benzene, thymol, carvacrol, mesitol, and the like. The latter class of magnesium phenolates we can utilize in accordance with this invention, that is, the magnesium polyhydric phenolates, is illustrated by the magnesium compounds derived from pyrocatechol and related polyhydric phenols wherein the aromatic nucleus is substituted with alkyl radicals such as methyl, ethyl, propyl, butyl, amyl, hexyl, octyl, decyl, and similar straight and branched chain alkyl radicals; and resorcinol including the analogous phenols wherein the aromatic nucleus is likewise substituted with alltyl radicals as previously indicated. Although the corresponding monohydric and {polyhydric thiophenols, that is, aromatic compounds wherein the aryl nucleus is substituted with at least one sulfhydryl group, form fuel soluble magnesium derivatives these are not preferred for utilization in accordance with the present invention because of the property of the sulfur contained therein of enhancing the destructiveness of organolead antiknock agents such as tetraethyllead. In addition to this, the use of sulfur-containing magnesium materials in accordance with this invention is to be avoided because of other deleterious effects upon the combustionprocess attributable to the presence ofsulfur in the fuel charge.

"Another embodiment er thisinvention m na r utiliz- "ing as organic magnesium material magnesium alcoholates, that is,magnesium compounds formed by the replacement of hydrogen in the hydroxyl groups of alcohols. When employing magnesium alcoholates we prefer magnesium compounds derived from alcohols 'con- "'taining' from about 10 to about 30 carbon atoms 'in the molecule. 'Thus, we prefer to employ the magnesium alcoholates derived from such alcohols as the straight and branched chain forms of decyl, undecyl, dodecyl, cetyl, ceryl, octac os anol, triacontanol, and likewise, the mag- "ne'sium alcoholates derived from the diverse 'p'olyhydric "alcohols containing from about 10 to about 30 carbon atoms in the molecule.

Another embodiment of the present invention is to utilize in combination with organolead-containing material magnesium chelates, that is, magnesium-containing compounds formed with substances possessing'a molecular structure inwhich a ring can be formed by the residual valencies or unshared electrons of neighboring atoms.

Hence, the magnesium chelates we employ in accord- ""ance' with our invention are preferably the magnesium "compounds formed with bidentate chelating agents which comprise one acidic group and one coordinating group.

i More specifically, the chelating agents we utilize in the formation of the organic magnesium material used in accordance with this invention comprise 1,3-diketones,

acid, diesters of malonic acid and alkyl and aryl substituted malonic acid, tetraesters of ethanetetracarboxylic acid, etc. Magnesium chelates derived from aromatic o-hydroxy aldehydes are illustrated by the magnesium chelates formed with salicyl aldehyde, and like materials. Para-methoxy o-hydroxy acetophenone and'similar materials serve as illustrations of o-hydroxy acetophenones which likewise form chelates with magnesium and which can be utilized in accordance with the present invention.

The employment of the organic magnesium material in organolead-containing material in accordance with the present invention is susceptible of variation.

In one embodiment of this invention we blend an organic magnesium compound of the character described hereinbefore with a liquid hydrocarbon fuel which has previously been treated in the normal fashion with a conventional amount of an organolead antiknock agent or organolead-containing antiknock fluid. The resulting homogeneous improved fuel composition can then be introduced into an internal combustion engine with the sion or minimization of deposit-induced autoignition. A variant of this procedure encompassed by the present invention comprises blending with a fuel of the gasoline boiling range a suitable quantity of an organic magnesium material as described hereinbefore, thereby formsubsequently can be treated with a typical organolead antiknock composition. A third variant in this procedure consists of concurrently blending both an organoleadcontaining composition and an organic magnesium material with a fuel for spark fired internal combustion engines. Upon stirring, shaking or otherwise agitating the resulting mixture, there is provided an improved fuel composition of the present invention possessing the characteristics of virtually eliminating wild ping. A preferred embodiment of the present invention, however, consists ofproviding improved antiknock fluids comprising an bigarioleadj antiknock agent and an organic' nia'gnesiuni material.'"That"isfto say, we prefer to provide a' composition of matter 'comprising'an org'anolead antikno'ck'agent such as a lead alkyl, and an organiemagn'esium'wompound formed with a material selected fromthe'class consisting of organic acids, phenols, alcohols and chelates. As indicated previously such a composition can I likewise contain the normal halide scavenger complement react with the lead, which quantity is two atoms of bromine per atom of'lead. In contrast, when the fluid is to 1 be employed in fuel for automotive and truck engines,

theory of chlorine as ethylene dichloride.

it is eflicaciou's to'employ a mixture of bromine and' chlorine scavengers such as for example a mixture consisting of 0.5 theory of bromine as ethylene dibromide' and 1.0 In addition to the'halide scavengers the improved antiknock fluids of the present invention, that is, those containing an organic "magnesium compound formed with a member selected from the class consisting of chelating agents and organic compounds containing a replaceable hydrogen in an hydroxyl'group, can contain other constituents such as organic dyes forproduct identification, solubilizingagents and/ or protective agents such as metal deactivators, antioiiidants, and the like. In this embodimentof our invention the improved antiknock fluid so' provided can be blended'with fuel of the gasoline boilingrange' thereby providing an improved composition particularly'from the standpoint of deposit-induced autoig'n'ition. The amount of the organic magnesium material we employ in the diverse compositions of the present invention is contingent upon, first, the nature of the--'magnesium compound employed and, second, the nature of the medium or vehicle in which it is to be employed. Generally speaking, however, we have found that depositinduced autoignition can be minimized significantly by providing compositions containing organic magnesium material and organolead compounds such that the'magnesium-todeadatom ratio isbetween about 0.001 to 1 and about 4 to 1. However, in general we prefer to employ the organic magnesium material in anamount such that the magnesium-to-lead atom ratio is'between about 0.01 to 1 and about 3 to 1, with the best overall results being obtained with a ratio between about Oil to 1 and about 1.2 to 1. Thus, when employing tetraethyl attendant marked uuppresmg a homogeneous magnesium-containing fuel which lead-containing improved antiknock fluids of the"pre'sent invention in fuel for internal combustion engines weblend therewith an amount'equivalent to from between'about 0.5 and about 6.0 milliliters of tetraethyllead per gallon. Generally speaking, when we employ other organoleadcontaining improved antiknock fluids of the present inventionfthat is, fluids comprising 'organic magnesium material and orga'n'olead antiknock agents such as tetraphenyllead and lead alkyls exemplified by tetram'ethyl- 'lead, tetrapropyllead, tetrabutyllead, dimethyldiethyllead, and other so-called mixed lead alkyls, in fuels for use in automotive engines the amount of such fluid'used is up to about 3.17 grams of lead per gallon. When such fluids are to be utilized in fuels for aviation engines the amount of lead blended therewith is up to about 634 grams of lead per gallon. Satisfactory results, however, ca'ngenerally be obtained with somewhat lesser quantities of organolea'd antiknock agent in the fuel. Thus, in automotive fuels and in particular, those adapted for use in high'compre'ssion engines it is usually necessary to utilize at least 2.1 grams of lead per gallon as a magnesiumcontaining antiknock fluid of the present invention. In

many instances somewhat greater proportions of lead are "required because of the relatively lower intrinsic: antiv knock value of the fuel. Under such circumstances we 'find that the addition of about 2.6 grams or more 'of'lead per gallon as an antiknock fiuidof the present invention results in an efficacious fuel. Likewise, fuels for modern aviation engines should contain at least about 4.7 grams of lead per gallon of our improved antiknock fluids.

A feature of this invention is that the above defined magnesium-to-lead ratios of the organolead-containing compositions of the present invention are critical. That is to say, We find that lesser quantities of magnesium in the compositions of the present invention, or in other words, compositions comprising a lower magncsium-tolead ratio than described hereinabove are virtually inefiective with regard to the suppression or elimination of wild ping. As a result of our concerted investigation with regard to the elfectiveness of magnesium when employed in accordance with the present invention we have developed two theories explaining in at least a tenable manner, this unexpected phenomenon. One explanation is that the important benefits derived from the presence of magnesium in the organolead-containing fluids or fuels of the present invention are contingent upon a requisite atmosphere upon combustion. In other words, this Wild ping suppressing atmosphere enveloping the normally active deposits necessitates the presence of a critical magnesium-to-lead atom ratio which apparently prevents the deposits in the combustion chamber from exerting their adverse catalytic activity. Another tenable explanation is that magnesium exerts its beneficial influence by modifying the deposits in some currently on explainable manner. In such a case, it will be apparent that the rate of deposition under present day engine operating conditions necessitates the presence of the above defined magnesium-to-lead atom ratio. According to this hypothesis the rates of physical scavenging whereby the deposits are physically broken away from the engine surfaces and chemical scavenging whereby volatile compounds are formed in the presence of halogen scavengers apparently are exceeded by the rate of magnesium deposition when our critical ratios are employed without significant changes in the amount of deposits so modified. Either or both of these explanations as to the effectiveness of the compositions of our invention find support in the fact that the addition of lesser quantities of magnesium to the fuel directly or by means of the organolead fluid compositions results in no noticeable improvement with regard to wild ping even when the engine is operated for long periods of time.

In contrast with the foregoing, we have found that the addition of organic magnesium compounds in amounts in excess of the above defined ratios results in a number of other difliculties, particularly during engine operation. For example, excessive amounts of organic magnesium compounds tend to increase the volume of deposits in the combustion chamber and on other engine parts such as pistons, valves, spark plugs and the like. This deposition undoubtedly is a contributing factor in the increase in the octane requirement of the engine resulting from the utilization of excessive amounts of magnesiumcontaining material. Similarly, under these circumstances deposits are frequently formed in the intake manifold and occasionally in the carburetor. These probably result from the differences in volatility between the major portion of the fuel and the organic magnesium material. However, when such material is utilized in accordance with the instant invention, that is, when the magnesium-tolead atom ratio is maintained between 0.001 to 1 and 4 to 1, both deposit-induced autoignition and detonation are obviated without the attendant difliculties described above, namely, increased deposition and octane requirement of the engine.

As indicated hereinbefore, the organic magnesium compounds present in the improved fuels and fluids of this invention are essentially sulfur-free. There are a number of reasons for this feature of our invention, among them the inherent properties of most sulfur-containing compounds of destroying the antiknock eifectiveness of organolead antiknock agents, of increasing the amount of engine deposits and their characteristics thereby resulting in increases in octane requirement, and of increasing the tendencies of antiknock fluids and fuels of deteriorating, particularly on storage in contact with meta lic containers, thereby enhancing the formation of gums, varnishes, sludge and the like. However, when utilizing organic magnesium material in accordance with the present invention, none of these deleterious effects are encountered.

To demonstrate the eflectiveness of the improved antiknock fluids and fuels of the present invention in the prevention, control, and minimization of deposit-induced autoignition we subject both hydrocarbon fuel treated in accordance with our invention and another portion of the same hydrocarbon fuel treated with a conventional antiknock mixture to a test procedure involving the use of a single cylinder CPR knock test engine equipped with an L-head cylinder and a Wild ping counter which records the total number of wild pings which have occurred during the test periods. Such apparatusincludes an extra spark plug used as an ionization gap which is installed in a second opening in the combustion chamer. Mechanical breaker switch driven at camshaft speed is also provided which, when closed makes the wild ping counter ineffective for the duration of the normal flame in the combustion chamber. The breaker is open for crankshaft degrees between 70 BTC (before top dead center) and 10 ATC (after top dead center). If a flame front induced early in the cycle by deposits reaches the ionization gap during this open period, the counter registers a wild ping regardless of the audible manifestations. During normal combustion with ignition timing at TDC (top dead center), the flame front reaches the ionization gap 15 to 18 AT C during the period wherein the points are closed and no count is made. The actual test procedure consists essentially of operating the test engine initial-1y having a clean combustion chamber under relatively mild cycling conditions for deposit formation until an equilibrium with regard to deposit-induced autoignition is reached. The effect of fuels treated in accordance with the instant invention is determined by comparing the test results obtained using the fuel treated with an organic magnesium material with those obtained using a fuel treated with a conventional antiknock mixture. Since the Wild ping counter records the total number of wild pings which have occurred during the test procedures a quantitative expression for the amount of deposit-induced autoignition is the number of wild pings per hour of operation.

The effectiveness of our improved fuel compositions in virtually eliminating deposit-induced autoignition will be apparent from the following specific examples.

Example I To gallons of a commercially available blend of straight run, catalytically cracked and polymer blending stocks was added and thoroughly mixed 300 milliliters of tetraethyllead as an antiknock fluid comprising tetraethyllead, 0.5 theory of bromine as ethylene dibromide, and 1.0 theory of chlorine as ethylene dichloride. The resulting homogeneous fuel composition was divided into two equal portions, one of which was used as the fuel in the previonsly designated single-cylinder laboratory test engine to formulate a base line on wild ping with a conventional fuel. To the other portion of the fuel composition was added an amount of magnesium octyl acetoacetate such that the resulting fuel after intimate mixing contained 0062 part of magnesium per gallon. Stated differently, the improved fuel composition so formed possessed a magnesium-to-lead atom ratio of 0.17 to 1. When the same engine was operated on this fuel it was found that there were 26 wild pings per hour of engine operation as contrasted with 118 wild pings per hour with the conventional fuel. Thus, the utilization of an improved fuel "and 1.0 theory of chlorine as ethylene dichloride.

resulting homogeneous fuel composition was then treated composition of the present invention 'resulted in' a reduction of 78 percent in the rate of Wild ping.

Exam 12 II i 50 gallons of a commercially available blend of straight run, catalytically cracked and polymer blending stocks. Upon mechanically agitating the resulting mixture a homogeneous fuel composition was prepared which con- 'tained 0.18 part of magnesium per gallon. The laboratory single-cylinder test engine as described hereinbefore was then operated on this improved fuel composition while contemporaneously determining the rate of wild pings as detected by the wild ping counter. It was found that the incorporation in the fuel of an improved antiknock fluid of the present invention resulted in 13 wild pings per hour as contrasted with a conventional lead-containing fuel which produced 118 wild pings per hour. Consequently, the improved fuel composition of the present invention resulted in a reduction of wild ping of- 89 percent.

Example III cent in the rate of wild'ping.

Exan'zp'le V An improved antiknock fluid composition of the pres ent invention was prepared by adding to 150 milliliters of tetraethyllead as an antiknock fluid comprising tetraethyllead, 0.5 theory of bromine as ethylene dibromide, 1.0 theory of chlorine as ethylene dichloride and 198 parts of magnesium oleate. A homogeneous fluid composition was obtained b y intimately mixing the aforementioned components such that the magnesium-to-lead ato'm ratio was 0.48 to l. The entire quantity of the improved antiknock fluid composition so prepared was added to 50 gallons of a commercially available blend of straight run, catalytically cracked and polymer blending "stocks. Upon mechanically agitating the resulting mixture a homogeneous fuel composition was prepared which contained 0.18] part of 'm'a gnesium per gallon. The laboratory single-cylinder test engine as described hereinbefore was then operated on this improved fuel composition while contemporaneously determining the rate of wild pings as detected by the wildping counter. It was found that the incorporation in the fuel of an improved anti- 'knock fluid of the present invention resulted in 32'wild pings per hour as contrasted with a conventional leadcontaining fuel which produced 118 wild pings per hour. Consequently, the improved fuel composition of the present invention resulted in a reduction of wild ping of 73 To 50 gallons of a commercially available blend of straight run, catalytically cracked and polymer blending stocks was added and thoroughly mixed 150 milliliters of tetraethyllead as an antiknock fluid comprising tetraethyllead, 0.5 theory of bromine as ethylene dibromide, The

with magnesium octyl acetoacetate, which treatment consisted of blending an amount of the magnesium compound with the conventional leaded fuel such that a engine on this fuel which possessed a magnesium-to-lead homogeneous fuel composition containing 0.36 part of 9 percent. I

Example VI An improved antiknock fluid composition of the present invention was prepared by adding to 150 milliliters of tetraethyllead as an antiknock fluid comprising tetraethyllead, 0.5 theory of bromine as ethylene dibromide, 1.0theo'ry of chlorine as ethylene dichloride and 5 parts of magnesium oleate. A homogeneous fluid composition was 'obtained by intimately mixing the aforementioned components such that the magnesium-to-lead atom ratio was 0.013 to 1 The entire quantity of the improved antiknock fluid composition so prepared was added to 50 gallons of acommercially available blend of straight run,

" catalytically cracked and polymer blending stocks. Upon atom ratio of 0.97 to 1 resulted in 14 Wild pings per hour whereas the conventional fuel produced 117 wild pings per hour. Thus, the combustion of an improved fuel composition of the present invention resulted in a'redu-ction of 88 percent in the rate of wild ping.

Example IV the previously designated single-cylinder laboratory test engine to formulate a base line on wild ping with a conventional fuel. position was added 66 parts of magnesium oleate, The resulting fuel composition was intimately mixed thereby producing a homogeneous composition containing 0055 part of magnesium per gallon, or stated differently, the improved fuel composition possessed a magnesium-tolead atom ratio of 0.15 to 1. When the same'engine was operated on this fuel it was found that there were 22 wild pings per hour of engine operation as contrasted with 116 wild pings per hour with the conventional fuel. Thus, the utilization of an improved fuel composition of To the other portion of the fuel com- "tected by the wild ping counter. incorporation in the fuel of an improved antiknock fluid mechanically agitating the resulting mixture a homogeneous. fuel composition was prepared which contained 0.005

part 'of magnesium per gallon. The laboratory singlecylinder test engine as described hereinbefore was then operated on this improved fuel composition while contemporaneously determining the rate of wild pings'as de- It was found that the of the present invention resulted in 73 wild pings per hour as contrasted with a conventional lead-containing fuel which produced wild pings per hour. Consequently,

, the improved fuel composition of the present invention resulted in a reduction of wild ping of 39 percent.

Example VII An improved antiknock fluid composition of th epi'esent invention was prepared by adding 19.5 partsof magnesiurn naphthenate to milliliters of tetraethylle'ad as an antiknock fluid comprising tetraethyllead, 0.5 theory of bromine as ethylene dibromide, and 1.0 theory of chlorine as ethylene dichloride. A homogeneousfluid composimechanically agitating the resulting mixture a homogeneous fuel composition was prepared which contained 0.024 part of magnesium per gallon. The laboratory singlecylinder test engine as describedjhereinbefore was then 75 operated on this improved fuel'composition 'while con- 1 1 temporaneously determining the rate of wild pings as detected by the wild ping counter. It was found that the incorporation in the fuel of an improved antiknock fluid of the present invention resulted in 37 wild pings per hour. Another identical amount of the same fuel base stock was treated with 150 milliliters of tetraethyllead as an :antiknock fluid comprising tetraethyllead, 0.5 theory of bromine as ethylene dibromide, and 1.0 theory of chlorine as ethylene dichloride. It was found that this fuel composition resulted in 120 wild pings per hour. Consequently, the improved fuel composition of the present invention resulted in a reduction of wild ping of 69 percent.

Example VIII To 100 gallons of a commercially available blend of straight run, catalytically cracked and polymer blending stocks was added and thoroughly mixed 300 milliliters of tetraethyllead as an antiknock fluid comprising tetraethyllead, 0.5 theory of bromine as ethylene dibromide,

and 1.0 theory of chlorine as ethylene dichloride. The resulting homogeneous fuel composition was divided into two equal portions, one of which was used as the fuel in the previously designated single-cylinder laboratory test engine to formulate a base line on wild ping with a conventional fuel. To the other portion of the fuel composition was added 195 parts of magnesium naphthenate. The resulting fuel composition was intimately mixed thereby producing a homogeneous composition containing 0.25 part of magnesium per gallon, or stated differently, the improved fuel composition possessed a magnesiumtolead atom ratio of 0.67 to 1. When the same engine was operated on this fuel it was found that there were 22 wild pings per hour of engine operation as contrasted with 120 wild pings per hour with the conventional fuel. Thus, the utilization of an improved fuel composition of the present invention resulted in a reduction of 81 percent in the rate of wild ping.

The preceding specific examples are merely illustrative of the beneficial effects produced by the improved organolead-containing compositions of the present invention. As indicated hereinbefore our invention is susceptible of a number of important embodiments by virtue of its great diversity of application. However, in essence the present invention consists of providing compositions comprising organolead-containing materials and an organic material wherein magnesium is bonded indirectly to the carbon residue or organic portion of the compound through a linking element. Thus, as indicated previously the organolead-containing materials which can be treated in accordance with the instant invention include leaded fuel for internal combustion engines, notably leaded aviation and automotive fuel and antiknock fluids, that is, compositions which generally consist of an organolead antiknock agent in combination with at least one halide scavenging material. in the latter embodiment of the present invention advantages are sometimes to be derived from cutting back the amount of such halide scavenger whereas in other instances the utilization of somewhat greater amounts of scavenging material than those conventionally used is etficacious. By the same token the halide scavengers so used are generally ethylene dibromide and/ or ethylene dichloride although it is to be understood that the improved fluid and fuel compositions of the present invention can contain other scavengers such as, for example, those disclosed in U. S. 1,592,954; 1,668,022; 2,364,921; 2,398,281; 2,479,900; 2,479,901; 2,479,902; 2,479,903; and 2,496,983. Likewise, the essentially sulfur-free organic magnesium material can be used in organolead-containing compositions in conjunction with other wellknown motor fuel adjuvants such as antioxidants, organolead stabilizers, organic dyes, solubilizers, and indeed with other organometallic materials frequently employed in fuel. Another variant inherent in the present invention which is frequently of economic significance is the fact that we can employ mixtures of diverse organic magnesium materials of the character described hereinbefore. This will become apparent by virtue of the relatively large number of mixtures of organic compounds containing replaceable hydrogen atoms in hydroxyl groups which are readily available as articles of commerce.

To further illustrate the beenficial effects provided by the compositions of the present invention upon wild ping, we find that this phenomenon is markedly reduced or virtually eliminated by utilizing in a magnesium-to-lead atom ratio between about 0.001 to 1 and 4 to 1 such mixtures as magnesium caproate and tetraethyllead, magnesium pelargonate in combination with tetraphenyllead, magnesium margarate with tetraethyllead, magnesium laurate in combination with tetrapropyllead, magnesium cerotate with tetrabutyllead, magnesium undecylenate in combination with tetraphenyllead, magnesium elaidate with tetrabutyllead, magnesium ricinoleate with tetraethyllead, magnesium geranate in combination with tetraethyllead, magnesium brassidate with tetramethyllead, magnesium sebacate in combination with tetraphenyllead, magnesium suberate with tetraethyllead, magnesium azelate with tetrabutyllead, magnesium ethanetetracarboxylate in combination with tetraethyllead, the magnesium salt formed from the diethyl ester of ethanetetracarboxylic acid and tetraphenyllead, magnesium methyl benzoate in combination with tetraethyllead, magnesium cinnamate in combination with tetrabutyllead, magnesium dimethyl benzoate and tetramethyllead, magnesium atropate with tetrapropyllead, magnesium naphthenate in combination with tetraethyllead, magnesium rosin acid derivative and tetraphenyllead, magnesium abietate with tetraethyllead, magnesium phenolate formed with o-cresol and tetraethyllead, magnesium phenolate formed with 1,2-dimethyl-3-hydroxy benzene and tetraphenyllead, magnesium phenolate formed with carvacrol and tetraethyllead, magnesium alcoholate and derived from decyl alcohol in combination with tetraphenyllead, magnesium alcoholate derived from cetyl alcohol with tetrabutyllead, magnesium alcoholate derived from cetyl alcohol with tetrabutyllead, magnesium alcoholate derived from undecyl alcoholin combination with tetraethyllead, magnesium chelate formed with ben zoyl acetone in combination with tetrabutyllead, magnesium chelate formed with hexyl acetoacetate and tetraethyllead, and the like.

Having fully described the nature of the present invention, the need therefor, and the best modes devised for carrying it out, we do not intend that our invention be limited except within the spirit and scope of the appended claims.

We claim:

1. Gasoline containing an antiknock quantity of a hydrocarbon lead antiknock agent, said quantity being up to about 6.34 grams of lead per gallon of said gasoline, and a gasoline-soluble, sulfur-free organic magnesium compound containing only the elements magnesium, carbon, hydrogen and oxygen, the magnesium being bonded to the organic portion of the molecule through oxygen, said compound being selected from the group consisting of (A) magnesium salts of 1) saturated monobasic hydrocarboaliphatic carboxylic acids, (2) monobasic unsaturated aliphatic carboxylic acids, (3) dibasic aliphatic acids,

(4) polybasic aliphatic acids, (5) aromatic carboxylic acids, (6) naphthenic acids, (7) rosin acids, (8) monohydric phenols, (9) polyhydric phenols; said acids and said phenols containing up to about 30 carbon atoms in the molecule; (B) magnesium alcoholates made from alcohols containing from about 10 to about 30 carbon atoms in the molecule, and (C) magnesium chelates made from bidentate chelating agents which contain one acidic group and one coordinating group and which contain up to about 20 carbon atoms in the molecule; said compound being present in amount such that the magnesium-to-lead atom ratio is between about 0.001 to l and about 4 to 1.

2. The gasoline composition of claim 1 wherein said magnesium-to-lead atom ratio is between about 0.01 to 1' and about 3 to 1.

3. The gasoline composition of claim 1 wherein said magnesium-to-lead atom ratio is between about 0.1 to l and about 1.2 to 1.

4. Gasoline containing an antiknock quantity of tetraethyllead, said quantity being from between about 2.1 and about 6.3 grams of lead per gallon of said gasoline, about 0.5 theory of bromine as ethylene dibromide, about 1.0 theory of chlorine as ethylene dichloride, and magnesium naphthenate present in amount such that the magnesium-to-lead atom ratio is between about 0.1 to 1 and about 1.2 to 1.

5. Gasoline containing an antiknock quantity of tetraethyllead, said quantity being from between about 2.1 and about 6.3 grams of lead per gallon of said gasoline, about 0.5 theory of bromine as ethylene dibromide, about 1.0 theory of chlorine as ethylene dichloride, and magnesium octyl acetoacetate present in amount such that the magnesium-to-lead atom ratio is between about 0.1 to 1 and about 1.2 to l.

6. Gasoline containing an antiknock quantity of tetraethyllead, said quantity being from between about 2.1 and about 6.3 grams of lead per gallon of said gasoline, about 0.5 theory of bromine as ethylene dibromide, about 1.0 theory of chlorine as ethylene dichloride, and magnesium oleate present in amount such that the magnesiumto-lead atom ratio is between about 0.1 to 1 and about 1.2 to 1.

7. An antiknock composition adapted for use as an additive for gasoline consisting essentially of a hydrocarbon lead antiknock agent and a gasoline-soluble, sulfurfree organic magnesium compound as defined in claim 1,

said compound being present in amount such that the magnesium-to-lead atom ratio is between about 0.001 to 1 and about 4 to 1.

8. An antiknock composition adapted for use as an additive for gasoline consisting essentially of tetraethyl- 1 14 lead, organic halide scavenger in amount suflicient to effectively reduce the amount of deposits formed in the engine, and a gasoline-soluble, sulfur-free organic magnesium compound as defined in claim 1, said compound being present in amount such that the magnesium-to-lead atom ratio is between about 0.1 to 1 and about 1.2 to 1.

9. Gasoline containing an antiknock quantity of tetraethyllead, said quantity being up to about 6.34 grams of lead per gallon of said gasoline, organic halide scavenger in amount sufiicient to effectively reduce the amount of deposits formed in the engine, and a gasoline-soluble, sulfur-free organic magnesium compound as defined in claim 1, said compound being present in amount such that the magnesium-to-lead atom ratio is between about 0.1 to 1 and about 1.2 to 1.

l0. Gasoline containing an antiknock quantity of tetraethyllead, said quantity being from between about 2.1 and about 6.3 grams of lead per gallon of said gasoline, about 0.5 theory of bromine as ethylene dibromide and about 1.0 theory of chlorine as ethylene dichloride, and a gasoline-soluble, sulfur-free organic magnesium compound as defined in claim 1, said compound being present in amount such that the magnesium-to-lead atom ratio is between about 0.1 to 1 and about 1.2 to 1.

11. The composition of claim 7 wherein said magnesium-to-lead atom ratio is between about 0.01 to 1 and about 3 to 1.

12. The composition of claim 7 wherein said magnesium-to-lead atom ratio is between about 0.1 to 1 and 1.2 to- 1.

References Cited in the file of this patent UNITED STATES PATENTS 1,916,735 MacLean et a1. July 4, 1933 2,151,432 Lyons et a1 Mar. 21, 1939 FOREIGN PATENTS 525,890 Great Britain Sept. 6, 1940 

1. GASOLINE CONTAINING AN ANTIKNOCK QUANTITY OF A HYDROCARBON LEAD ANTIKNOCK AGENT, SAID QUANTITY BEING UP TO ABOUT 6.34 GRAMS OF LEAD PER GALLON OF SAID GASOLINE, AND A GASOLINE-SOLUBLE, SULFUR-FREE ORGANIC MAGNESIUM COMPOUND CONTAINING ONLY THE ELEMENTS MAGNESIUM, CARBON, HYDROGEN AND OXYGEN, THE MAGNESIUM BEING BONDED TO THE ORGANIC PORTION OF THE MOLECULE THROUGH OXYGEN, SAID COMPOUND BEING SELECTED FROM THE GROUP CONSISTING OF (A) MAGNESIUM SALTS OF (1) SATURATED MONOBASIC HYDROCARBOALIPHATIC CARBOXYLIC ACIDS, (2) MONOBASIC UNSATURATED ALIPHATIC CARBOXYLIC ACIDS, (3) DIBASIC ALIPHATIC ACIDS, (4) POLYBASIC ALIPHATIC ACIDS, (5) AROMATIC CARBOXYLIC ACIDS, (6) NAPHTHENIC ACIDS, (7) ROSIN ACIDS, (8) MONOHYDRIC PHENOLS, (9) POLYHYDRIC PHENOLS; SAID ACIDS AND SAID PHENOLS CONTAINING UP TO ABOUT 30 CARBON ATOMS IN THE MOLECULE; (B) MAGNESIUM ALCOHOLATES MADE FORM ALCOHOLS CONTAINING FROM ABOUT 10 TO ABOUT 30 CARBON ATOMS IN THE MOLECULE, AND (C) MAGNESIUM CHELATES MADE FROM BIDENTATE CHELATING AGENTS WHICH CONTAIN ONE ACIDIC GROUP AND ONE COORDINATING GROUP AND WHICH CONTAIN UP TO ABOUT 20 CARBON ATOMS IN THE MOLECULE: SAID COMPOUND BEING PRESENT IN AMOUNT SUCH THAT THE MAGNESIUM-TO-LEAD ATOM RATIO IS BETWEEN ABOUT 0.001 TO 1 AND ABOUT 4 TO
 1. 